JPH0486648A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photosensitive material small in processor pick-offs by covering a polyester film support with a copolymer of vinylidene chloride and specifying all the hydrophilic colloidal layers on the side of emulsion layers. CONSTITUTION:This photographic silver halide sensitive material has one or more gelatin-containing hydrophilic colloidal layers including at least one photosensitive silver halide emulsion layer on the polyester film support coated with the vinylidene chloride copolymer, and all the hydrophilic colloidal layers on the side of the emulsion layers contain gelatin in an amount of >=12 wt.% and 2.0 - 4.0 g/m<1>, thus permitting the obtained silver halide photographic sensitive material to be superior in rapid processing aptitude, and small in pinhole- like defects occurring at the time of processing (processor pick-off).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, which has particularly excellent suitability for rapid processing and which is free from pinhole-like defects (processor pick-offs) in blackened areas that occur during processing.
The present invention relates to a silver halide photographic light-sensitive material having a low amount of pick-off (also called pick-off). The present invention can be used, for example, in the field of fluorescent materials for X-rays.

(Prior art) In recent years, high-temperature and rapid processing has become popular in the developing process of photographic materials. It has rapidly become popular, and the processing time for processing various photosensitive materials using automatic processors has been greatly shortened.

In order to achieve high-temperature, rapid processing, we need a developer that can achieve sufficient sensitivity in a short time, a sensitive material that has excellent developability and does not leave any residual color even during short processing times, and dries quickly after washing with water. A sensitive material is required. Many automatic processors have a built-in drying zone, and if the drying of the photosensitive material is poor,
Automatic processors are required to have a higher drying capacity, which forces them to be larger. Furthermore, as a result of generating a large amount of heat, there are also problems such as an increase in the temperature of the room in which the automatic processor is installed.

To prevent this from happening, photosensitive materials are designed to dry as quickly as possible.

An effective method is to add a sufficient amount of hardening agent during the coating process of the photosensitive material, and to reduce the amount of swelling of the emulsion layer and surface protective layer during the constant development and water washing process, thereby starting drying. It is known to reduce the water content in the previous photosensitive material and to reduce the amount of coated gelatin. However, sensitive materials with a reduced amount of coated gelatin have the disadvantage that pinhole-like defects in blackened areas called processor pick-offs increase during development processing.

(Object of the Invention) An object of the present invention is to provide a silver halide light-sensitive material with less processor pick-off even when the amount of gelatin is reduced so as to be able to withstand a rapid processing time in which the total processing time is 15 to 60 seconds. .

DISCLOSURE OF THE INVENTION The above object of the present invention is to provide a hydrophilic colloid containing one or more layers of gelatin on at least one side on a polyester film support, including at least one light-sensitive silver halide emulsion layer. In a silver halide photographic light-sensitive material having a layer, the polyester film support is coated with a copolymer layer containing vinylidene chloride, and the entire hydrophilic colloid layer on the side containing the silver halide emulsion layer contains a high molecular weight component. This is achieved by a silver halide photographic light-sensitive material comprising gelatin containing 12% by weight or more of gelatin and having an amount of gelatin of 2.0 g to 4.0 g/if.

As the vinylidene chloride copolymer undercoated polyester support used in the present invention, Japanese Patent Application No. 62-36244, No. 6
3-174698 is useful.

That is, the vinylidene chloride copolymer in the present invention is 7
Copolymer containing 0 to 99.5% by weight, preferably 85 to 99% by weight of vinylidene chloride, JP-A-51-135
Vinylidene chloride/acrylic ester/as described in No. 526
A copolymer made of a vinyl monomer having an alcohol in the side chain, a copolymer made of vinylidene chloride/alkyl acrylate/acrylic acid described in U.S. Pat. Examples include a copolymer of vinylidene chloride/acrylonide/itaconic acid, and a copolymer of vinylidene chloride/alkyl acrylate/itaconic acid described in US Pat. No. 3,788,856. Specific examples of compounds include the following.

All numbers in parentheses represent weight ratios.

Copolymer of vinylidene chloride dimethyl acrylate: hydroxyethyl acrylate (83:12:5) Copolymer of vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (82:10:8) Vinylidene chloride: hydroxydiethyl methacrylate (
92: Copolymer of 8) vinylidene chloride:butyl acrylate:acrylic acid (9)
4:4:2) copolymer of vinylidene chloride:butyl acrylate:itaconic acid (7
5: 20: 5) copolymer of vinylidene chloride: methyl acrylate: itaconic acid (9,0: 8: 2)
Copolymer of vinylidene chloride: methyl acrylate dimethacrylic acid (93: 4: 3) vinylidene chloride: monoethyl itaconate (96
: 4) copolymer vinylidene chloride:acrylonitrile:acrylic acid (96
:3. Copolymer of vinylidene chloride dimethyl acrylate: acrylic acid (90:5:5) Copolymer of vinylidene chloride: ethyl acrylate: acrylic acid (90:5:5)
2:5:3) copolymer vinylidene chloride:methyl acrylate-co-3-chloro-2
-Hydroxypropyl acrylate (84:9:
7) copolymer of vinylidene chloride; methyl acrylate; copolymer of diN-ethanol acrylamide (85: 10: 5); vinylidene chloride, dimethyl methacrylate: acrylonitrile (85: 8); 90: 7: 3) Vinylidene chloride dimethyl methacrylate: acrylonitrile (92: 5: 3) In the present invention, the vinylidene chloride copolymer consists of a core-and-L type latex, and the core has the following general formula (1). ) and (II), and the cough shell has at least one type of repeating unit represented by the following general formula (1).
), (I[[) and (IV) each preferably has at least one type of repeating unit.

I +CH2-C-÷ (n) COOA'' N /A +CH-C÷ (TV) A' Ah In the above formula, the vinylidene chloride copolymer in the present invention has the general formula n) to (TV) relative to vinylidene chloride. Seven Tsuma indicated by
It is preferable to combine at least one of each of these with zero to several types of arbitrary molmers as necessary.

The core portion of the vinylidene chloride copolymer latex of the present invention accounts for 60 to 95 wt% of the total latex particles, especially 70 to 9
It is preferable that it is Qwc%, and the Ner portion is 5 to 4Q.
It is preferably 10 to 30 wt%, particularly 10 to 30 wt%.

The ratio (W) of the portion consisting of repeating units represented by general formula (1) in the entire latex particle is 70 to 98.5
wt%, preferably 85 to 97 Wj%, most preferably 88 to 94 wt%.

The ratio (X) of the portion consisting of repeating units represented by the general formula (ff) is 1.0 to 20 wj%, preferably 2 to 1
2 wt%, particularly preferably 5 to 10 wt%.

Represented by the general formula (I[[), the ratio (y) of the portion consisting of repeating units is 0.1 to 5.Qwt%, preferably 0.
3 to 3.5% by weight, particularly preferably 0.5 to 2.5% by weight, and the ratio (z) of the portion consisting of repeating units represented by general formula (IV) is 0.05 to 3.5% by weight. Ojl amount%, preferably 0.1-1. 5% by weight, particularly preferably 0.
It represents 1 to 0.81if%.

In general formulas (n) to (IV), AI is preferably a hydrogen atom, a methyl group, or a CI or F atom, more preferably a hydrogen atom or a methyl group.

A2 preferably represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and more preferably represents an unsubstituted alkyl group having 1 to 4 carbon atoms.

A3 represents a hydrogen atom or a methyl group.

A4 is preferably a hydrogen atom, a methyl group, -CH2C0O
It represents an H group, particularly preferably a hydrogen atom or a methyl group.

As preferably represents a hydrogen atom.

A6 preferably represents an alkoxycarbonyl group or an N-alkylcarbamoyl group having a -COOH group or a -coon group, particularly preferably a -Cool group.

Examples of substituents for the substituted alkyl group, substituted alkoxy group, or phenyl group represented by A2 and A6 include an alkoxy group (which may be further substituted with several alkoxy groups), a halogen atom, a nitro group, and a cyan group. , an alkyl group (in the case of a phenyl group), a carbonamide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonic acid group, and the like.

Next, specific examples of monomers of general formulas (n) to (IV) will be given, but the present invention is not limited thereto.

n-I CH2=CH COOCR2 U 2 GHz=CH COOCt Hs I[-3 CHz=CHCHs COOC-CH+ CH's 0OCH2 COOC2R5 COO(n-)Cz H? CHI =C-CH YuN IV-1 CH, =CH 00H COOCHs 0OH COOCF+ OOH 0OH (Cis or trans) COOCHz CR20CH* ■-10 cHt =CH COOCHz CH! OCH3 II[-1 CH=CH 0OH CONHCHI R2 OOH N IV-6CH2=CH C00CH2CH200CCH2CH2COOHTV-
Other specific examples of 7CH=CH CHff C00H -a formula (If) include the following.

n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 3-acryloylpropanesulfonic acid, acetoxyethyl acrylate, phenyl acrylate, 2-methoxyacrylate, 2-ethoxyacrylate, 2-(methoxyethoxy)ethyl acrylate, 2-methanesulfone Amidoethyl acrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, dimethylethylaminomethacrylate.

Examples of other optional salts used in the present invention include crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, acrylamides, methacrylamides, vinyl ethers, styrenes, etc. can be mentioned.

Furthermore, monomers of the general formula (I[[), (TV)) may be used for the core portion, and monomers of the general formula (n) may be used for the shell portion.

More specific examples of these monomers include butyl crotonate, hexyl crotonate, and the like as crotonate esters. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, and the like. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include diethyl itaconate, dimethyl itaconate, dibutyl itaconate, and the like. Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, isopropylacrylamide, n-butylacrylamide, hydroxymethylacrylamide, diacetone acrylamide, acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, and the like.

Examples of methacrylamide include methylmethacrylamide,
Ethyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, 2-methoxyethyl methacrylamide, dimethyl methacrylamide,
Examples include diethyl methacrylamide. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene,
Examples include chloromethylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, fromstyrene, vinylbenzoic acid methyl ester, 2-methylstyrene, styrene sulfonic acid, vinylbenzoic acid, trimethylaminomethylstyrene, etc. .

Examples of other monomers include allyl compounds (such as allyl acetate), vinyl ketones (such as methyl vinyl ketone), and vinyl heterocyclic compounds (such as vinyl pyridine).
, unsaturated nitriles (eg, acrylonitrile, methacrylonitrile, etc.).

It may also be a monomer having a group that binds to the binder directly or via a curing agent, such as an active methylene group, (poly)hydroxyphenyl group, sulfinic acid group, or an amino group (substituted with an alkyl group or phenyl group). ), an active ester group, an active halogen atom, an active vinyl group and its precursor, an epoxy group, an ethyleneimine group, and the like.

The vinylidene chloride copolymer of the present invention can be synthesized using an emulsion polymerization method, but as an emulsion polymerization method, techniques disclosed so far, such as US Pat.
No. 4,401.788, No. 4.446.273, No. 4. 535i No. 120, JP-A-61-108
No. 650, No. 62-2, ) No. 6871, No. 62-246
No. 913, No. 62-246912, No. 57-1391
No. 36, No. 61-236669, No. 57-13710
A synthesis method similar to No. 9 etc. can be used. According to these synthesis methods (for example, synthesis according to JP-A No. 62-256871), a polymer with excellent adhesion or shear stability is distributed in the shell part, and a polymer that ensures barrier properties is distributed in a part of the core. The present invention was achieved using vinylidene chloride latex obtained by synthesizing.

Here, the polymer with excellent adhesion, etc. of the present invention is one obtained using at least one of each of (1), (III), and (TV), and the polymer that ensures barrier properties is one obtained by using at least one of (1), (III), and (TV). , (I[), respectively.

The emulsifier used in the synthesis of the present invention may be anionic, nonionic, cationic, hetain, polymeric surfactant, or a mixture thereof, but anionic emulsifiers are preferred. Among anionic emulsifiers, those containing at least one kind of alkyl hanzene sulfonate are particularly preferred, with an average number of about 11 to 16), (m is 10.12.14.16 or 1B), etc. can be mentioned.

The method of coating the polyester support with the vinylidene chloride copolymer latex in the present invention includes well-known coating methods such as dip coating, air knife coating, curtain coating, roller coating, and wire bar coating. Coating can be performed by a cord method, a gravure coating method, or an extrusion coating method using a hopper as described in US Pat. No. 2,681.294.

In order to further improve the adhesive strength between the polyester support and the above polymer layer, the surface of the polyester support is subjected to chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, and activated plasma. process,
High pressure steam treatment, desorption treatment, laser treatment, mixed acid treatment,
There is no problem with treatment such as ozone oxidation treatment.

Further, in order to firmly adhere the polymer layer used in the present invention to the polyester base, US Pat. No. 3.245,
No. 937, No. 3,143,421, No. 3,501.3
As described in No. 01, No. 3,271,178, phenol, resorcinol, O-cresol, m-cresol, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid! It is necessary to add a swelling agent for the polyester such as , water loral, benzyl alcohol, etc. As these swelling agents, resorcinol is preferably used, but resorcinol has the drawback of often inducing spot failures during the manufacturing process.

A particularly preferred method for avoiding such drawbacks is to apply the polymer layer used in the present invention after subjecting the surface of the polyester support to glow discharge treatment.

The glow discharge treatment in the present invention refers to any conventionally known method, for example, Japanese Patent Publication No. 35-7578, No. 3
No. 6-10336, No. 45-22004, No. 45-2
No. 2005, No. 45-24040, No. 46-4348
No. 0, U.S. Patent No. 3057.792, U.S. Patent No. 3,057.
No. 795, No. 3.179,482, No. 3,288.6
No. 38, No. 3,309,299, No. 3,424.73
No. 5, No. 3.462.335, No. 3. 475. 3
No. 07, No. 3,761,299, British Patent No. 997.0
No. 93, JP-A-53-129262, etc. can be used.

The appropriate pressure during glow discharge is O, OO5 to 20 Torr, preferably 0.02 to 2 Torr. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may even destroy the object to be treated. Discharge is generated by applying a direct voltage between one or more pairs of metal plates or metal rods placed with a space between them in a vacuum tank. This voltage can take various values depending on the composition and pressure of the atmospheric gas, but normally within the above pressure range it is 500 to 500.
Stable fixing glow discharge occurs within 5ooov.

A particularly suitable pressure range for improving adhesion is 20
00 to 4000V.

Furthermore, as seen in the prior art, the discharge frequency ranges from DC to several 100,100 O, preferably from 50 Hz to 20 M.
Hz is appropriate. Regarding the discharge treatment strength, 0.0 IKV・A・min/bore is used because the desired adhesive performance can be obtained.
5 KV-A-min/I, preferably 0.05 KV-A-min/m-I KV-A-min/m' is suitable.

Furthermore, in order to improve the adhesive strength between the polyester support and the above polymer layer, a layer having adhesive properties to both may be provided as an undercoat layer.

As such an undercoat, water-soluble polyester, urethane compounds, etc. can be used.

Also, commercially available anchor coating agents such as Vylon (manufactured by Toyobo Co., Ltd.), Jurimer (manufactured by Nippon Junwara Co., Ltd.), Polysol (manufactured by Showa Kobunshi Co., Ltd.), etc. may be used.

The coating solution of vinylidene chloride copolymer in the present invention includes:
Compounds commonly referred to in the art as curing agents can be included. For example, U.S. Patent Box 3.325.28
No. 7, same 3. 288. No. 775, 3.549.3
77, Hergie Patent No. 6.602,226, etc.; U.S. Patent Box 3.291.624
No. 3232.764, French Patent Box 1.543
694, British Patent Box 1,270.578, etc.; US Patent Box 3,091.537
Epoxy compounds described in U.S. Pat. No. 49-26580; vinyl compounds described in U.S. Pat. Examples include ethyleneimine compounds described in No. 549,378, and methylol compounds.

Among these curing agents, triazine compounds, dialdehyde compounds, and epoxy compounds are preferably used.

The amount of these curing agents added is 0.001 to 30 g per 11 coating liquid of vinylidene chloride copolymer.

The thickness of the vinylidene chloride copolymer layer in the present invention is 0.
1μ or more and 5μ or less, preferably 0°2μ or more and 1.
A value in the range of 0 or less is used.

In the present invention, polyester refers to a polyester whose main components are aromatic dibasic acid and glycol. Typical dibasic acids include terephthalic acid, isophthalic acid, p-
β-oxyethoxybenzoic acid, diphenylsulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, diphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, etc. Glycols include ethylene glycol, propylene glycol, butanediol, neopentylene gellicol, 1゜4-cyclohexanediol, 14-cyclohexane dimetatool,
Examples include 1,4-bisoxyethoxybenzene, bisphenol A1 diethylene glycol, and polyethylene glycol.

Among polyesters made of these components, polyethylene terephthalate is the most convenient from the viewpoint of availability.

There is no particular limit to the thickness of polyester, but it is approximately 12μ.
A thickness of about 500 μm, preferably about 40 μm to 200 μm is advantageous in terms of ease of handling and versatility. In particular, biaxially stretched crystallized materials are advantageous in terms of stability, strength, and the like.

In order to improve the adhesive strength between the polymer layer and the emulsion layer, a layer having adhesive properties to both may be provided as an undercoat layer. In order to further improve the adhesion, the surface of the polymer layer may be subjected to conventional pretreatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

The hydrophilic colloid binder used in the entire hydrophilic colloid layer on the side containing the silver halide emulsion layer of the present invention is
It is gelatin containing 12% by weight or more, preferably 14% by weight or more of a high molecular weight component as described in Japanese Patent No. 2-87952.

The ratio of high molecular weight components of gelatin in the present invention is determined by gel permeation, chromatography (rG
PC method).

The conditions for the GPC method are shown below.

a, Column: G5-620 (manufactured by Asahi Kasei Corporation), length 500
m, temperature 37°C1 φ7.6 cabinet x 3 bottles 0 Separated liquid: 0.05M, NatT (PO4KHz
PO4 aqueous solution, flow rate 1 vol/++1n C1 detector: Ultraviolet absorption spectrophotometer (UVn wavelength 254
nm) Sample for d0 analysis: Absolute amount of gelatin 0.4 μg The horizontal axis shows the retention time (Retention Tf
e) In the 020 curve obtained by plotting the optical intensity on the vertical axis, the peak at the exclusion limit first appears, then the β component of gelatin,
A peak that seems to be the α component appears, and as the retention time further increases, the tail becomes narrower. In the present invention, the proportion of the high molecular weight component is the proportion of the area of the peak at the exclusion limit to the total area. It is obtained by calculating.

Specifically, the 0 that appears at about 25 minutes of lychinsilane time.
A perpendicular line is drawn from the minimum point of the 20 curve to the horizontal axis, and the ratio of the area of the portion to the left of the perpendicular line (high molecular weight component) to the total area is calculated.

Regarding the general manufacturing method of gelatin, it is known that
For example, T.H. James (T.

The Theory of the Photographic Process, by James F.
f thePhotographic Process
) 4th edition, 1977 [Macmilla
n) Publishing], p. 55, Chemical Photography Handbook (Part 1), 72-75
Page (Maruzen Co., Ltd.), Makoto Kikuchi, Photo Chemistry, 1976
It is described in 1955 (Kyoritsu Shuppan), p. 213, Akado, Part 4, Edited by Mizushima, Part 3, Protein Chemistry, 1955 (Kyoritsu Shuppan), p. 453.

For example, lime-processed gelatin is made as follows. First, cow skin and bones are soaked in saturated lime water for 2 to 3 months to remove keratin, etc., then washed with water, neutralized, and extracted in hot water at about 60°C for 6 to 8 hours (1 2nd extraction at about 65°C, 3rd extraction at 75°C, and finally 4th extraction by heating near the boiling point. After extraction, filter, and generally at 50°C under reduced pressure. Concentrate as follows, cool and solidify at around 10°C, and dry at around 25°C.

For example, the following method can be used to produce gelatin containing a large amount of high molecular weight components according to the present invention.

(2) In the extraction operation in the above manufacturing method, use the gelatin extract described after extraction to eliminate the gelatin extract at the initial stage of extraction.

(2) In the above manufacturing method, the processing temperature is kept below 40°C in the manufacturing process from extraction to drying.

■ Dialyze the gelatin gel in cold water (15°C).

[The Journal of Photography Inc. Science]
aphicScience), Volume 23, Page 33 (197
See 5)].

■Fraction method using isopropyl alcohol [Discussions Op the Faraday Society (
Discussions of the Farada
ySociety), vol. 18, p. 288 (1954)].

By using the above methods alone or in combination, the gelatin of the present invention having a high molecular weight component of 12% by weight or more can be obtained.

Hydrophilic colloids other than gelatin can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate, dextran, and starch derivatives; A variety of synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl and lolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

In addition to lime-processed gelatin, acid-processed gelatin and Bulletin of the Society of Scientific Photography Japan (Bull)
, Soc, Sci, Phot, Japan)k
16.30 (1966) may be used, and gelatine hydrolysates and enzymatically decomposed products may also be used.

Next, the silver halide grains used in the present invention include silver chloride,
Any silver halide consisting of chlorine, bromine, or iodide may be used, such as silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide, but especially silver bromide, Silver iodobromide, silver chloride,
Silver chlorobromide and silver chloroiodobromide are preferred. The silver iodide content in the silver halide is preferably 0 to 20% by mole, particularly preferably 0 to 10%.

The particle shape may be so-called regular particles having regular crystal bodies such as cubes, octahedrons, and tetradecahedrons, and may also be potato-shaped, spherical, plate-shaped, tabular with a particle diameter of 5 times or more the particle thickness, etc. It may also be one with an irregular crystal shape or a composite thereof.

The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution.

The silver halide emulsion layer used in the present invention is not limited to one layer, but may have two or more layers, and two or more types of emulsions with different grain sizes, sensitivities, etc. may be mixed or used in separate layers. . Further, the emulsion layer is not limited to one side of the support, but may be provided on both sides.

These photosensitive emulsions may be mixed with a substantially non-photosensitive emulsion (for example, an internally fogged fine grain emulsion), or may be used by coating them in separate layers.

Furthermore, even if the crystal structure of silver halide grains is similar up to the inside, there are also grains with a layered structure with different inside and outside, British Patent No. 635,841, US Patent No. 3,6
It may also be of a so-called conversion type as described in No. 22.318. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used.

The emulsion of the present invention can contain heavy metal ions such as iridium ions. Incorporation of iridium ions is achieved by adding a water-soluble iridium compound (for example, hexachloroiridate (I[[) acid salt, hexachloroiridate (rV) acid salt)] in the form of an aqueous solution during emulsion preparation.

It may be added in the same aqueous solution form as the silver halide for grain formation, or it may be added before grain formation, during grain formation, or after grain formation until chemical aggravation.
Particularly preferred is addition during particle formation.

During the formation of silver halide grains, for example, ammonia, rhodanpotash, rhodanammonium, thioether compounds, 1,000-ion compounds, amine compounds, etc. can be used as silver halide solvents to control grain growth.

In addition to the silver halide solvent, compounds that control crystal habit by adsorbing to the grain surface, such as aninine-based aggravating dyes, tetrazaindene-based compounds, and mercapto compounds, can be used during grain formation.

Silver halide emulsions can be prepared using the commonly used chemical sensitization method.
For example, various chemical sensitization methods such as gold sensitization, sulfur sensitization, reduction sensitization, and thioether compound sensitization are commonly used.

The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral enhancing dye, if necessary. Spectral sensitizing dyes that can be used include, for example, Hamer, "Heterocyclic Compounds: The Cyanine Soybean and Related Compounders", John Wiley and Sump (1964), (F, M
, Hamer”Heterocyclic Comp
ounds The Cyanine Dyes an
dRelated Compounds”, John
Wiley & 5ons (1964) and Starmer, Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry, John Wiley & Sump (197).
7th edition) D., M., Sturmer, 'Heter.
ocyclic Compounds -5peci
al Topics in Heterocyclic
ChemistryJohn Wiley & 5
cyanine, merocyanine, logocyanine, styryl, hemicyanine, oxonol, hengelidene, holopolar, etc., which are described in Ons (1977), etc., can be used, and cyanine and merocyanine are particularly preferred.

Sensitizing dyes that can be preferably used in the present invention include JP-A-60-13'3442, JP-A-61-75339, and JP-A-6
No. 2-6251, No. 59-212827, No. 50-1
Examples include cyanine dyes and merocyanine dyes represented by the general formulas described in No. 22928 and No. 59-1801553. Specifically, Japanese Patent Application Laid-Open No. 60-133442
pages (8) to (11) of JP-A-61-75339, pages (24)-(25) of JP-A-61-75339, page (24)-(25) of JP-A-62-6251. Pages 10) to (15), pages (5) to (7) of JP-A-59-212827, JP-A-5
No. 0-122928, pages (7) to (9), JP-A-59
Enhancing dyes that spectrally sensitize silver halide in the blue region, edge region, red region, or infrared region of the spectrum, which are described in pages (7) to (18) of No. 180553, can be mentioned. Representative examples of infrared aggravating dyes are described in Japanese Patent Application No. 63-96476.

These sensitizing dyes may be used alone or in combination, and combinations of enhancing dyes are often used particularly for the purpose of hyperchromatic enhancement. Along with the enhancing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, a nitrogen-containing heteroartic ring. Aminostilbene compounds whose nuclear group is W-substituted (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635.72)
No. 1), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc., U.S. Pat. No. 3,615,613. , 3rd and 6th
15. ．． No. 641, No. 3,617,295, No. 3
．． The combinations described in No. 635,721 are particularly useful.

The above sensitizing dye is 5 x 10-7 per mole of silver halide.
mol-5X10-" mol, preferably 1x10-6 mol-1X10-" mol, particularly preferably 2XIO-6-5
It is contained in the silver halide photographic emulsion layer in a proportion of X10-' moles.

The sensitizing dyes described above can be dispersed directly into the emulsion layer. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution. Further, as a method for adding the aggravating dye, US Pat. No. 3,469.9
Dissolving a dye in a volatile organic solvent, dispersing this solution in a hydrophilic colloid, as described in the specification of No. 87, etc.
Method of adding this dispersion to an emulsion, Japanese Patent Publication No. 46-24
A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 61-45217, etc.; A method of mechanically crushing and dispersing a dye in an aqueous solvent and adding this dispersion to an emulsion: A method of dissolving a dye in a surfactant as described in U.S. Pat. No. 3,822.135. , a method of adding this solution into an emulsion;
A method of dissolving a left-shifting compound using a left-shifting compound as described in JP-A No. 51-74624, and adding this solution to an emulsion, A method of dissolving the compound in an acid-free acid and adding this solution to an emulsion is used. Other additions to emulsions include U.S. Patent Nos. 2.912.343 and 3.3.
No. 42.605, No. 2,996.287, No. 3,
The method described in eg No. 429,835 can also be used. The enhancing dyes described above may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but can, of course, be dispersed at any stage of the preparation of the silver halide emulsion.

For example, it may be carried out during or before chemical amplification, or during or before the formation of silver halide grains according to US Pat. No. 4,183,756 and US Pat. No. 4,225,666. It is known that if a sensitizing dye is added during or before chemical sensitization, or during or before grain formation, the sensitizing dye will be strongly adsorbed to silver halide. The residual color of window materials using the silver halide hole side can also be improved without any problem.

The above-mentioned aggravating dyes may be used in combination with other sensitizing dyes. For example, U.S. Patent Nos. 3703.377, 2.688,545, and 3,397.060.
No. 3.615.635, No. 3.628.96
4, British Patent No. 1.242.588, British Patent No. 1.29
No. 3.862, Special Publication No. 43-4936, No. 44-14
No. 030, No. 43-10773, U.S. Patent No. 3,41
No. 6.927, Japanese Patent Publication No. 43-4930, U.S. Patent No. 2
．． No. 615.613, No. 3.615632, No. 3
．． 617.295, 3635.721, etc. can be used.

Various compounds can be added to the photographic window optical material of the present invention in order to prevent a decrease in intensity and the occurrence of fog during the manufacturing process, storage, or processing of the optical window material. These compounds are nitrohenzimidazur, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a
, 7-titraazaindene, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, and many other compounds have been known for a long time. An example of a compound that can be used is "The Theo" by C. E. K. Mees.
ryof the Photographic Pro
cess'' (3rd edition, 1966) pp. 344-349
For example, U.S. Patent No. 2
．． Thiazolium salts described in 13I, 038 and 2.694,716; U.S. Patent No. 2.88
Azaindenes described in 6°437 and 2,444,605; U.S. Patent No. 3.287135
Urazol neck described in U.S. Patent No. 3.
Sulfocatechols described in British Patent No. 236゜652, etc.; oxime compounds described in British Patent No. 623,448, etc.;
Mercaptotetrazoles, nitrones, and nitroindazoles described in U.S. Pat. No. 6.897 and U.S. Patent No. 3,397.987;
etal 5 alts) ; U.S. Patent No. 3220.8
Thiuronium salts (thiu
ronjum 5 alts) ; U.S. Patent No. 2.56
Examples include salts of palladium, platinum, and gold, which are described in No. 6.263 and No. 2 597.915.

The silver halide photographic material of the present invention includes developing agents such as hydroquinones; catechols; aminophenols; 3-pyrazolidone; ascorbic acid and its conductor; reductones and phenylenedi7mine E; or a combination of developing agents, which can be incorporated into the silver halide emulsion layer and/or other photographic layers (e.g. protective layers, interlayers, filter layers, antihalation layers, backing layers, etc.). can. The developing agent can be dissolved in a light-transmitting solvent or as described in U.S. Patent No. 2,592.368 or French Painting Patent H1.
, 505,778.

In the present invention, as a matting agent, U.S. Patent No. 2.992
, No. 101, No. 2,701.245, No. 4,14
Homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid as described in No. 2,894 and No. 4.396.706 Organic compounds such as starch, silica, titanium dioxide, sulfuric acid, strontium, barium, etc. The particle size for which fine particles of inorganic compounds can be used is 1.0 to 10,
In particular, it is preferable that the number of houses is 2 to 5.

The surface layer of the photographic light-sensitive material of the present invention may contain silicone compounds described in U.S. Pat. No. 3,489,576, U.S. Pat.
In addition to the colloidal silica described in the publication, paraffin wax, higher fatty acid ester, starch conductor, etc. can be used.

The hydrophilic colloid in the constituent layers of the photographic material of the present invention includes:
Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be added as a tumescent agent.

Further, the hydrophilic colloid layer of the photographic material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. Examples of the polymer include a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid, and styrene. -Butadiene copolymers, polymers or copolymers consisting of monomers having active methylene groups can be preferably used.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardening agents, such as aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, methyloldimethylhydantoin, etc.),
Dioxane visiting conductors (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,35-triacryloyl-hexahydro-S-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-(β)
-(vinylsulfonyl)propionamide), etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. alone or in combination. Can be used. Among them, JP-A-53-
No. 41220, No. 53-57257, No. 59-162
546, 60-80846 and the active halides described in U.S. Pat. No. 3,325,287 are preferred.

The silver halide photographic material of the present invention may have a light-sensitive silver halide emulsion layer, a back layer, a surface preservation layer, an intermediate layer, an antihalation layer, and other non-photosensitive layers.

There may be two or more silver halide emulsion layers, and the sensitivity, gradation, etc. of the two or more silver halide emulsion layers may be different.
Further, one or more silver halide emulsion layers or non-photosensitive layers may be provided on both sides of the support.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention contains a coating aid, 'f'! Various surfactants may be included for various purposes such as prevention, improvement of slipperiness, emulsification dispersion, prevention of adhesion, and improvement of photographic properties (for example, acceleration of development, increase in contrast, sensitization).

Examples of the surfactant used in the present invention include "Surfactants and Their Applications" by Ryohei Oda et al. (A Shoten, 1964);
Hiroshi Horiguchi “New Surfactant” (Sankyo Publishing ■, 1975)
Or ``Mackation's Day Targent and E Marzifiers.''
Visions, MC Publishing Camba=-
1985) (r Me Cutcheon's De
tergants & Emulsifiers J
(MCCutcheonDivisions, McP
publishing Co., 1985)), Japanese Patent Application Laid-open No. 76741/1983, Japanese Patent Application No. 13398/1983,
It is described in No. 61-16056, No. 61-32462, etc.

It inhibitors include, among others, U.S. Pat. No. 4.201.58.
No. 6, JP-A-60-'80849, JP-A No. 59-7455
No. 4, Patent Application No. 60-249021, No. 61-3246
Fluorine-containing surfactant or polymer described in No. 2, JP-A-60-76742, JP-A-60-80846, JP-A-60
-80848, 60-80839, 60-76
No. 741, No. 58-208743, Patent Application No. 1988-13
No. 398, No. 61-16056, No. 61-32462
Nonionic surfactants described in JP-A No. 57-204540, Japanese Patent Application No. 61-3
Conductive polymer or latex (nonionic, anionic, cationic, amphoteric) described in No. 2462
The vine is preferably used.

Examples of inorganic antistatic agents include ammonium, alkali metal, and alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, acetates, phosphates, and thiocyanates. Composite oxides prepared by doping conductive tin oxide, zinc oxide, or these metal oxides with antimony or the like, as described in Japanese Patent No. 118242, etc., can be preferably used. Furthermore, various charged octagonal complexes, doping compounds of π-conjugated polymers, organometallic compounds, eyebrow compounds, etc. can also be used as antistatic agents, such as T CN
Examples include Q/TTF, polyacetylene, and polypyrrole. These are Morita et al., Chemistry and Industry 59 (3), 103
~111 (1985), Doiichiken (4), 146~1
52 (1985).

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a plasticizer, optical brightener, air fog inhibitor, color tone agent, etc.

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Various known infrared light sources such as mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, light emitting diodes, laser beams (e.g. gas lasers), dye lasers, YAG lasers, semiconductor lasers, etc.) Any light source can be used.

Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, T-rays, α-rays, or the like. The exposure time is 1/phenyl-4,4- which is usually used in cameras.
Examples include dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-phenyl4.4-dihydroxymethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminephenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminephenol, and N-(4-hydroxyphenyl)glycine. ,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.01 mol/λ to 1.2 mol/l.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. Sulfite is 0.2 mol/IL or more, especially 0.4 mol/J1
The above is preferable, and the upper limit is preferably up to 2.5 mol/11.

The pH of the developer used in the present invention is preferably in the range of 9 to 13, more preferably 10 to 12.
The range is up to

Alkaline agents used for setting pl() include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

Japanese Patent Application No. 1987-28708 (Borate), Japanese Patent Application No. 1988-
Buffers such as No. 93433 (eg, sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethyl formamide, methyl cellosolve, hexylene glycol, ethanol; Organic solvents such as methanol = 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-
Mercapto compounds such as sulfonic acid sodium salt, 5-
It may also contain antifoggants such as indazole compounds such as nitroindazole, benztriazole compounds such as 5-methylbenztriazole, and, if necessary, color toners, surfactants, antifoaming agents, water softeners, and other additives. It may also contain amino compounds described in JP-A-56-106244.

In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.

In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, F, A, Mason Chopsticks “Photographic
"Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Patent No. 2,1
No. 93,015, No. 2,592,364, Japanese Unexamined Patent Publication No. 4
Those described in No. 8-64933 may also be used.

In the present invention, a developer consisting of one agent containing the above-mentioned 3-pyrazolidone-based developing agent may be used by replenishing the developer. ~30g added, more preferably 0.5g~20g5 still more preferably 1g~1sg
f=added. Further, the above-mentioned one-component developer can be used in a concentrated form, and in that case, it is preferable to dilute the developer with water as the photographic material is processed.

The development temperature and time of the development process in the present invention are preferably about 5° C. to about 50° C. and 15 seconds or less, particularly preferably 30° C. to 40° C. and 6 seconds to 15 seconds.

The fixer used in the present invention is an aqueous solution containing thiosulfate and has a pH of 3.8 or more, preferably 4.2 to 5.5. More preferably the pH is 4.65 to 5.5.

Sodium thiosulfate and ammonium thiosulfate are available as fixing agents, but they contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.The amount of fixing agent used may be changed as appropriate. and generally about 0.1 to about 6 mol/I
It is L.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, ammonium sulfate, potassium alum, and the like.

In the fixing solution, tartaric acid, citric acid, gluconic acid, or conductor visiting agents thereof can be used alone or in combination of two or more kinds. These compounds are 0.0 per fixer IIL
Those containing 0.05 mol or more are effective, particularly 0.01 mol/1 and 0.03 mol/1.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ricic acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixer may optionally contain a preservative (e.g. sulfite, bisulfite) and a pH 13 buffer (e.g. acetic acid, boric acid).
, a pH adjuster (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-218562.

The fixing temperature and time are preferably 6 seconds to 1 minute at about 0°C to about 50°C, more preferably 6 seconds to 30 seconds at 30°C to 40°C, and still more preferably 6 seconds to 30°C to 40°C. 15
Seconds.

In the present invention, the fixer concentrate may be composed of a single agent if the fixer concentrate is replenished into the automatic processor along with water to dilute the photosensitive material as it is processed.

The fixer stock solution exists stably as a single agent at pH 4,
5 or more, more preferably pH 4.65 or more. This is because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfided, especially if the fixer is left for a long period of time before it is actually used. Followed by pH 4,
In the range of 5 or more, less sulfur dioxide gas is generated, which improves the production environment. Although the upper limit of pH is not so strict, if fixation is carried out at too high a pH, the pH of the membrane becomes high even after subsequent washing with water, and swelling becomes difficult.

Therefore, since the drying load becomes large, the pH is limited to about 7. In fixing solutions that use aluminum salts to harden films, the pH limit for preventing precipitation of aluminum salts is 5.5.

In the process of the present invention, either the developing solution or the fixing solution may be a so-called working solution that does not necessarily require dilution water as described above (that is, the undiluted solution is replenished).

The amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 1:0 to 8.
The total amount of each of the developing solution and fixing solution is preferably from 50 ml to xsoomU per 1 m' of light-sensitive material.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.

Any method known in the art can be used for the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water for washing water or stabilizing liquid, not only is it possible to save water by reducing the amount of replenishment to less than 31 per m' of photosensitive material, but it also eliminates the need for piping for installing an automatic processing machine. This makes it possible to further reduce the number of stock tanks. That is, the automatic developing machine can be made even more compact by supplying solution dilution water and washing water or stabilizing solution for the developer and fixer from a common single-layer stock tank.

When water treated with anti-I measures is used in combination with washing water or stabilizing liquid, the formation of limescale can be effectively prevented.
A water saving treatment of 0 to 3 p per m'', preferably 0 to 1° C. can be carried out.

Here, when the replenishment amount is 0, no replenishment is performed at all except for appropriately replenishing the amount of washing water in the washing tank that has decreased due to natural evaporation, etc. In other words, the so-called "reservation water" is essentially not refilled. Refers to cases in which a processing method is used.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated by the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and an even more significant stabilizing effect can be obtained. The amount of washing water is also much smaller than before.

When washing with a small amount of water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning mechanism as described in No. 68.

Furthermore, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with ice treated with preventive measures according to the treatment, is
As described in Japanese Patent No. 0-235133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that. This is more preferable because the stock water can be saved and the amount of waste liquid can be reduced.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986-
No. 253807, No. 60-295894, No. 61-6
The method using the antibacterial agent described in No. 3030 and No. 61-51395 can be used.

Furthermore, L, e, West"Water Qua
Photo Sci,
& Eng, Vol. 9 No. 6 (1965), M.
W, Beach “Microbiological
Growths in Motion-Picture
ProcessingSMPTE Journal
Vol, 85. (1976), R,0, Deega.
n.

Photo Processing Wash
Water BiocidesJ, Imaging
Tach, Vol 10. No. 6 (1984) and JP-A-57-8542, JP-A-57-58143, JP-A-58-105145, JP-A No. 5-132146, JP-A No. 5
B-18631, No. 57-97530, No. 57-1
Antibacterial agents and anti-inflammatory agents described in No. 57244 etc.
A surfactant or the like can also be used in combination.

In addition, the washing bath includes R.T., Kreiman, J.
, Image, Tech 10 (6), 242 (
RE is an isothiazoline compound described in 1984).
Isothiazoline compounds described in SEARCHDis (: LO5LIRE i205 volume, Item 20526 (May issue, 1981), same volume 228, Item
22845 (April issue, 1983), the compound described in Japanese Patent Application No. 61-51396, etc. are used as microbiocide.
It can also be used together as

Furthermore, specific examples of the anti-spill agent include phenol, 4-chlorophenol, pentachlorophenol, cresol, 0-phenylphenol, chlorophene, dichlorophene, formaldehyde, geltaraldehyde, chloracetamide, P-hydroxybenzoic acid ester, 2
-(4-thiazoline)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-phthalimide, 2,4.4'-)dichloro-2'-hydro Examples include oxydiphenyl ether.

It is preferable that the water treated with anti-mold measures and stored in a water stock tank be used both as dilution water for the undiluted solution of processing solutions such as the developer-fixer and as washing water, since it takes up less space. Preparation dilution water and washing water (
(or stabilizing liquid) and ゛ can be stored separately in separate layers, or only one of them can be taken directly from the tap.

When stored separately for different species, apply anti-mold measures and
The washing water (or stabilizing bath) can contain various additives.

For example, the chelate stability constant AogK with aluminum
A chelate compound having a value of 10 or more may be included.
These are effective in preventing scuttling in washing water when the fixing solution contains an aluminum compound as a hardening agent.

Specific examples of chelating agents include ethylenediaminetetraacetic acid (fLogK -16,1, the same applies hereinafter), cyclohexanediaminetetraacetic acid (17,6), diaminopropanoltetraacetic acid (13,8), diethylenetriaminepentaacetic acid (18, 4), triethylenetetraminehexaacetic acid (19,
7) and their sodium salts, potassium salts, and ammonium salts, and the amount added is preferably from 0.01 to
10 g/l, more preferably 0.1 to 5 g/fl.

Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing water droplet unevenness. Surfactants include cationic, anionic,
Either non-ionic type or amphoteric type may be used.

Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho Tara.

Various compounds are added to the stabilizing agent for the purpose of stabilizing the image. For example membrane p) adjust the I (e.g. p
H3-8) various ii buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide,
(Used in combination with sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.)
Typical examples include aldehydes such as and formalin. In addition, there are various f! Additives may be used, and the same or different desired compounds may be added to 2f! The above may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

Water washing or stabilization bath temperature and time by the above method is 0
6 seconds to 1 minute at ℃ to 50℃ is preferable, but 15℃ to 40℃
more preferably from 6 seconds to 30 seconds, and more preferably from 15°C to 4°C.
Qt is preferably 6 to 15 seconds.

The photographic material that has been developed, fixed, and washed is squeezed out of the washing water. That is, it is dried through a squeeze roller method. Drying is carried out at a temperature of about 0°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 100°C.
The time may be 1 minute, but it is more preferably about 5 seconds to 30 seconds at 40t to 80°C.

In the present invention, the so-called dry-to-dry processing time for development, fixing, washing, and drying is within 60 seconds, preferably within 50 seconds.

Here, "dry to dry" means that from the moment the tip of the window material to be processed enters the film insertion part of the automatic processing machine,
This refers to the time from when the image is processed until the moment the image emerges from the machine.

Preparation of Example Support-1 A first layer of undercoat having the following composition (a) was applied to a two-wheel stretched and oriented crystallized polyethylene terephthalate film (thickness 175μ) so that the dry film thickness was 0.5μ.
Dry at ℃ for 1 minute.

Composition - (a) Next, apply the undercoat liquid of the following composition - (b) to a dry film thickness of 0.1 μm.
Apply the second undercoat after drying at 120℃ for 1 minute.
formed a layer.

Composition (b) Support 1 was prepared by coating both sides of a polyethylene terephthalate support with the above formulation.

Preparation of support body 2 A semicircular rod electrode with a length of 40 holes and a diameter of 3G is 10a in cross section.
Four pieces were fixed on an insulating plate at n intervals. This electrode plate was fixed in a vacuum tank, and a two-wheeled stretched polyethylene terephthalate film with a thickness of 175μ and 30cI11 was placed on a rod 15cmN away from the electrode surface and directly facing the electrode surface for 20mI++.
The vehicle was run at a speed of /min. Immediately before the film passed over the electrode, a heating roll with a temperature controller and a diameter of 50 cm was set at 120° C., and the heating roll was arranged so that the film was in contact with the electrode. Glow discharge brings the inside of the tank to 0
, 2000 to the above electrode while maintaining I Torr.
This was done by applying a voltage of V. At this time, the electrode current was 0°5A. At this time, the PET support is 0.12
This means that 5KVA/d of processing has been received. An aqueous dispersion of a copolymer of vinylidene chloride/methyl acrylate/acrylic acid=90:5:5% by weight was applied onto the polyethylene terephthalate treated with glow discharge in this way.
A coating thickness of 5μ was applied. Furthermore, the following undercoating liquid - (C
) was applied to 20af#.

Undercoating liquid-(C) Both surfaces of a PET support were coated with the following formulation to prepare support-2.

(1) Preparation of silver halide emulsion Lime-treated gelatin was prepared by the method described in JP-A-62-87952. In this case, in the extraction operation, the gelatin extract in the late stage of extraction is used to eliminate the gelatin extract in the early stage of extraction, and the process temperature is kept below 40°C in the manufacturing process from extraction to drying. Gelatins A-E containing high molecular weight components as shown in Table 1 were prepared.

After adding a liquid equivalent amount of ammonia to a container heated to 55°C containing gelatin A, potassium bromide, and water, add a silver nitrate aqueous solution and a potassium bromide aqueous solution while maintaining the PAg value in the reaction container at 7.60. were added by a double jet method to prepare monodisperse silver bromide emulsion grains A having an average grain size of 0.55 μm. The emulsion grains are ±40% of the average grain size.
98% of the total number of particles were present within this range. After desalting this emulsion, the pH was adjusted to 6.2 and the PAg to 8.6, and then gold/sulfur sensitization was performed using sodium thiosulfate and chloroauric acid to obtain the desired photograph. The amount of Ag per 1 kg of emulsion was 100 g, and the amount of gelatin was 60 g.

The (100) plane/(111) plane pressure ratio of this emulsion was measured by the Kubelkamunk method and was found to be 98/2. This was named Emulsion A.

In the same way, using gelatin B-E, emulsion B-E
made.

(2) Preparation of emulsion coating solution Weigh 1 kg of each of emulsions A to E, dissolve them by heating in 40"C, and add a methanol solution of near-infrared sensitizing dye, structural formula S-1 (
9X10-'M/j Riwo 7 (ld, 4-hyr-droxy-6-methyl-1,3,3a, 7-titrazaindene aqueous solution, coating aid dodecylbenzenesulfonate aqueous solution, thickener polybotacium p - Emulsion coating solution A by adding an aqueous solution of a vinylbenzenesulfonate compound
-E was prepared.

(3) Preparation of coating solution for surface protective layer of photosensitive material layer A 10 wt % gelatin aqueous solution A-H consisting of gelatin A-E heated to 40°C, thickener polyethylene sodium sulfonate aqueous solution, matting agent polyester Methyl methacrylate fine particles (average particle size 3.0 μm), dura side N, N'-ethylene bis-(vinylsulfonylacetamide), fabric aid as mono-octylphenoxyethoxyethanesulfonate aqueous solution, polyethylene as antistatic agent. A coating solution was prepared by adding an aqueous surfactant solution and an aqueous solution of a fluorine-containing compound having the structure shown below.

CwF + ysOJ (CaB6) CHiCOOK
and CsF+ySOJ (CJJ(C1hCHz-0)
+5H (4) Preparation of back layer coating solution 1 kg of 10 wt% gelatin aqueous solution heated to 40°C
A compound (CH2)4 (CHz)4 so, e O3K having the following structure was added to the coating so that the coating amount was 70 Wg/rrf, and a thickener polyethylene sodium sulfonate aqueous solution and a hardening agent N were added.
, N'-ethylenebis-(vinylsulfonylacetamide) aqueous solution, and a coating aid sodium t-octylphenoxyethoxyethanesulfonate aqueous solution were added to prepare a back coating solution.

(5) Preparation of coating solution for the surface protective layer of the back layer A 10 wt% gelatin aqueous solution heated to 40°C, a binder polyethylene sodium sulfonate aqueous solution, and a matting agent polyethylene methacrylate fine particles (average particle size 3.0 μm)
A coating solution was prepared by adding an aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate as a coating aid, an aqueous polyethylene surfactant solution as an antistatic agent, and an aqueous solution of a fluorine-containing compound having the following structure.

CJlffSO! N(C3Hff)C1lICOOK and CIFIffSOJ(C311ff) (CHzC
Hz-0+-158 (6) Preparation of coating sample The above-mentioned back coating solution and back surface protective layer coating solution were coated on one side of Support-1 and Support-2 with a gelatin coating amount of 4 g/m. I applied it as desired.

The amount of gelatin in the surface protective layer of the bag is 1.0 g/m. Following this, emulsion coating solutions A-E containing near-infrared sensitizing dyes were applied to the opposite side of each support (coated silver amount was 3.5 g/rd; gelatin amount is shown in Table 1) to protect the surface of the sensitive material. Layers A to E (gelatin amount 1.0 g/rrf) were coated to create samples 1 to 13.

g Processor pick-off evaluation samples -1 and -2 were uniformly exposed to light with an amount of light sufficient to give 1 sax, and then exposed using an automatic photolithography machine manufactured by Fuji Photo Film ■.
f&IIPPM-9000, developer RD-7, fixer
35°C3P treatment using Fujij F (Dryto
Dry for 45 seconds).

The number of pinball-shaped white dots (processor pickoffs) generated in an area of 10 cm x 10 1 of blackened parts was calculated for Samples 1 to 13 with n=3.

Procedural amendment 4. Subject of amendment: Specification column "Detailed description of the invention" Display of incidents 1990 Patent Application No. 200992 name of invention Silver halide photographic material 3. Person who makes corrections Relationship with the incident

Claims (1)

[Scope of Claims] 1) A halogenated polyester film support having one or more gelatin-containing hydrophilic colloid layers, including at least one photosensitive silver halide emulsion layer, on at least one side of the polyester film support. In the silver photographic light-sensitive material, the polyester film support is coated with a copolymer layer containing vinylidene chloride, and the entire hydrophilic colloid layer on the side containing the silver halide emulsion layer on the support is highly 1. A silver halide photographic material comprising gelatin containing a molecular weight component of 12% by weight or more, and having a total coating amount of gelatin of 2.0 to 4.0 g/m^2. 2) The silver halide photographic material according to claim 1, which is automatically developed in a total processing time of 15 to 60 seconds.